Novel approaches to metal free catalysis

无金属催化的新方法

• 批准号: RGPIN-2021-02835
• 负责人: Fontaine, FrédéricGeorges
• 金额: $ 5.76万
• 依托单位: Université Laval
• 依托单位国家: 加拿大
• 项目类别: Discovery Grants Program - Individual
• 财政年份: 2022
• 资助国家: 加拿大
• 起止时间: 2022-01-01 至 2023-12-31
• 项目状态: 已结题
• 来源: https://www.nserc-crsng.gc.ca/ase-oro/Details-Detailles_eng.asp?id=748673
• 关键词: Novel; approaches; metal; free; catalysis

The research proposed here will explore boron architectures to develop innovative catalytic processes that offer unique reactivity not accessible to transition metal (TM) catalysts, notably in C-H functionalization processes. Our long-term goal is to refine this knowledge to develop unique catalytic concepts that will simplify catalyst development and for catalytic processes that will be readily usable by end users (academic and industrial researchers) at a minimal cost, while respecting the guidelines of green chemistry (solvent-free, no toxic by-products, simple synthesis). The first theme will involve developing the transfer borylation reaction to carry out the C-H borylation of alkenes and apply this method to generate interesting chemical motifs. The transfer borylation, a reaction we developed in our research group, consists in using one expendable arylboronate (Ar-B(OR)2) to borylate an arene (Ar'-H), releasing Ar-H and Ar'-B(OR)2. By avoiding species with B-H bonds during catalysis, we can borylate substrates that are otherwise challenging to borylate using traditional catalysts, such as the ones containing alkene, alkyne or carbonyl moieties. We also want to exploit the equilibrium observed between two different arylboronates in solution to design active boronate reagents that would increase the catalytic activity when used in substoichiometric amounts. In the second theme, we will develop algorithms that will allow a combinatorial computational approach to frustrated Lewis pair (FLP) chemistry and catalysts' discovery. Using our knowledge on the computational design of frustrated Lewis pair catalysts and localization-delocalization matrices, we will determine invariants that will describe the electronic and steric properties of FLPs. We will develop an algorithm that will use a database made of these invariants that will predict the nature of the interaction between a Lewis acid and a Lewis base and quickly predict the FLP reactivity of possible Lewis pairs. This method will be calibrated using calorimetric studies that we will carry out in our laboratory. The last theme consists in coordinating FLPs on carbon electrodes to modulate the electronic properties of catalysts without requiring structural modifications. We want to demonstrate that electrochemistry can be a tool to help quantify the steric hindrance of FLPs and modulate their reactivity. We will notably graft C-H borylation catalysts to look at the effect of electronic modulation on catalysis. We will also develop an electrochemical approach to quantify the steric properties of FLPs.

此处提出的研究将探索硼架构，以开发创新的催化过程，这些过程提供了无法通过过渡金属（TM）催化剂访问的独特反应性，尤其是在C-H功能化过程中。我们的长期目标是完善这些知识，以开发独特的催化概念，这些概念将简化催化剂的开发和催化过程，这些过程将以最低的成本（学术和工业研究人员）易于使用，以最低的成本可用，同时尊重绿色化学的准则（无溶剂无溶剂，无毒的毒性副产品，简单的合成，简单的合成）。 第一个主题将涉及开发转移的植物反应以进行烯烃的C-H型体，并应用此方法来产生有趣的化学基序。我们在研究小组中发展的反应转移boryation包括使用一种消耗的芳基硼酸盐（Ar-b（OR）2）来使芳烃（AR'-H）释放，释放Ar'-H和Ar'-B（OR）2。通过在催化过程中避免具有B-H键的物种，我们可以使用传统的催化剂（例如含有烷烃，碱或羰基部分的催化剂）来挑战型底物。我们还希望利用在溶液中观察到的平衡，以设计活性的硼酸酯试剂，这些试剂将增加催化活性，用于取代化学计量量。在第二个主题中，我们将开发算法，该算法将允许一种组合计算方法来挫败刘易斯对（FLP）化学和催化剂的发现。利用我们对沮丧的刘易斯对催化剂和定位 - 迁移式矩阵的计算设计的了解，我们将确定将描述FLP的电子和空间特性的不变性。我们将开发一种算法，该算法将使用由这些不变性的数据库，该数据库可以预测路易斯酸与刘易斯碱基之间相互作用的性质，并迅速预测可能的刘易斯对的FLP反应性。该方法将通过我们将在实验室中进行的量热研究进行校准。 最后一个主题包括在碳电极上协调FLP，以调节催化剂的电子特性而无需进行结构修饰。我们要证明，电化学可以是帮助量化FLP的空间障碍并调节其反应性的工具。我们将显着移植C-H型催化剂来研究电子调制对催化的影响。我们还将开发一种电化学方法来量化FLP的空间特性。